Composition of matter and method of making same



Patented Feb. 5, 1946 COMPOSITION or MATTER AND METHOD OF MAKING SAMEMelvin De Groote, University City, and Bernhard Keiser, Webster Groves,Mo., assignors to Petrolite Corporation, Ltd., Wilmington, Del., acorporation of Delaware No Drawing. Original application June 26, 1944,

Serial No. 542,235. Divided and this application February 23, 1945,Serial No. 579,500

6 Claims.

This invention relates to a new chemical product or composition ofmatter, our present application being a division of our co-pendingapplication Serial No. 542,235, filed June 26, 1944.

The main object of our invention is to provide a new chemical compoundor product that is particularly adapted for use as a demulsifier forcrude oil emulsions, but which is also capable of various other uses.

Another object of our invention is to provide a practicable method formanufacturing said new chemical product or compound.

The new material herein described, particularly when employed as ademulsifier, consists of sub-resinous reaction products derived byreaction between (A) A polybasic carboxy acid fractional ester having(a) an unreacted carboxyl radical; and (b) a detergent-formingmonocarboxy acid radical having at least 8 and not more than 32 carbonatoms; said detergent-forming acid radical being an integral part of adetergent-forming acid compound consisting of acids, monohydric alcoholesters and polyhydric alcohol esters; and

(B) A basic esterlfied amino-alcohol of the formula:

\N.R:.OOCRI in which R is a monovale'nt radical free from ether linkagesand having at least 8 carbon atoms and not more than 32 carbon atoms andbeing a member of the class consisting of aliphatic hydrocarbonradicals, alicyclic hydrocarbon radicals, and aralkyl hydrocarbonradicals; R2 is a divalent radical having less than 16 carbon atoms andnot more than 3 ether linkages and being a member of the classconsisting of alkylene radicals, hydroxyalkylene radicals, alkyleneoxyradicals, hydroxyalkyleneoxy radicals, polyglycol and hydroxy polyglycolradicals, in which any alkylene radicals present are selected from thegroup consisting of ethylene, propylene, butylene, and methylbutylene;and R1 is a monovalent radical and a member of the class consisting ofaliphatic hydrocarbon radicals, alicyclic hydrocarbon radicals andaralkyl hydrocarbon radicals having not more than 32 carbon atoms, andthe radical HORz, wherein R2 has its prior significance; R3CO is an acylradical of a low molal monocarboxy acid having less than 8 carbon atoms;with the added porviso that at least one of the three radicals R1, R2and Rs shall have present an alcoholic hydroxy radical. I

The amino nitrogen atom must be free from directly linked acyl radicalsor aryl radicals. Stated another way, the nitrogen atoms must be a basicamino nitrogen atom. See Textbook of Organic Chemistry, Richter, 2ndEdition, page 253.

Amines of the kind contemplated and used as reactants in producing thecompounds herein described, are produced in various manners. They may beproduced from naphthenic acids, resin acids, fatty acids, or oxidiedpetroleum acids, or the like, by converting the acid into the ester,preferably the ethyl ester, or the like, and then converting the esterinto the alcohol. Such alcohols, derived from various fatty acids,naphthenic acids, oxidized petroleum acids, resin acids, and the like,are available commercially and are employed in the manufacture ofwetting agents, or the like, by sulfating or sulfonating such alcohols.Such high molal alcohols can be converted into the chlorides, and thechlorides reacted with ammonia or a primary or secondary amine to giveamines of the type herein contemplated. If derived from higher fattyacids, such as stearic acid, the hydrocarbon chain is simply an alkylradical. Naturally, it derived from an -unsaturated fatty acid, such asoleic acid, the radical would represent an unsaturated hydrocarbonradical. I1. derived from rlcinoleic acid or some other hydroxy acid,such as hydroxystearic acid, such amines include a hydroxylatedhydrocarbon radical.

In actual practice amines oi the kind herein contemplated as reactants,can be obtained in various ways.

In view of what has been said, it will be noted that the groupintroduced into the amine and derived at least hypothetically from anacid, is really the carbon atom chain radical of the acyl group of theacid or hypothetical acid, along with what was at least hypotheticallythe carbonyl carbon atom. For the sake of convenience, this radical willbe referred to as a hydrocarbon radical; and it is intended to includederivatives in which a hydrogen atom or a small number of hydrogen atomshave been replaced by the hydroxyl radical; for instance, the hydroxyhydrocarbon radical which would be supplied by ricinoleic acid,hydroxystearic acid, dihydroxystearic acid, or the like. In the presentinstance such usage seems eminently correct, in that the hydrocarbonradical supplies the hydrophobe portion of the amine, and thishydrophobe portion is not changed markedly by the presence of one or twohydroxyl groups, as are present in the case of ricinoleic acid,hydroxystearic acid, or the lie; and such hydroxyl groups areessentially non-functional, in that they are not necessarily relied uponto supply points of chemical activity, as far as the herein contemplatedcompounds are concerned. They mayslightly decrease the hydrophobecharacter of the radical to some degree: but this cannot be significant.and can be appreciated by reference to ricinoleic acid. Since the carbonatom chain supplied to the amine by means of ricinoleic acid has 18carbon atoms, it would appear relatively immaterial whether there waspresent one hydroxyl group or not. Thus, it is to'be borne in mind thatthe use in the hereto appended claims of the word hydrocarbon isintended to include the hydroxy-hydrocarbon type of the kind in whichthe hydroxyl group does'not materiallyreduce the hydrophobe character ofthe hydrocarbon group, as, for example, the group or radical which wouldbe obtained from ricinoleic acid. I

In addition to synthetic carboxy acids obtained. by the oxidation ofparaffins, or the like, there is the somewhat analogous class obtainedby treating carbon dioxide or carbon monoxide in the presence ofhydrogen or an oleflne, with steam, or by causing a metallic alkoxide,or a halogenated hydrocarbon to react with chloracetic acid, or withpotassium cyanide, and saponifying the product thus obtained. Suchproducts or mixtures thereof, having at least 8 and not more than 32carbon atoms and having at least one carboxy group or the equivalentthereof, are as suitable for use as the conventional detergent-formingmonocarboxy acids, and another analogous class equally suitable, is themixture of carboxylic acids obtained by the alkali treatment of alcoholsof higher molecularweight formed in the catalytic hydrogenation ofcarbon monoxide. The, synthetic carboxy acids so obtained can beconverted into high molal amines by. the same procedure as employed forthe conversion of other carboxy acids.

The patents previously referred to indicate a large number of suitableamines which are the type previously specified. For the sake of brevity,

reference will be made only to certain primary amines. Obviously,secondary or tertiary amines could be derived from such primary aminesby introducing alkyl groups having less than 8 carbon atoms, such asmethyl, ethyl, propyl, butyl groups and the like; or one might introduceradicals in which the carbon atom chain was interrupted at least once byoxygen, as, for example,

radicals derived by reacting an amine with compounds, such asCzHsOCzHsCl or OHC2H4OC2H4C1.

An aralkyl group, such as a benzyl group, might be introduced, or analicyclic group, such as a cyclohexyl group. i

The primary amines which may be used as such or converted into secondaryamines, include the following: Octadecenylamine, cetylamine,stearylamine, oleoamine, ricinoleoamine, amines derived from naphthenicacids, amines derived from octadecadiene 9,11'-acid-1,' octadecylamine,amines derived from mixed unsaturated fatty acids such asjs 'oy'abeanfatty acids, cottonseed oil fatty acids, linseed oil fatty acids,heptadecylamine, hexadecylamine, dodecylamine, decylamine, etc.

Having obtained amine of the kind described, such aminesare treated withan oxyalkylating agent, preferably ethylene oxide. Otheroxyalkylatingagents may be used. As typical examples of applicablecompounds may be mentioned ep chlorhydrin, glycide alcohol, ethyleneoxide, propylene oxide, butene-2 oxide, butene-l oxide, isobutyleneoxide,butadiene oxide, butadiene dioxide, chloroprene oxide, isopreneoxide, decene oxide, styrene oxide,.cyclohexylene oxide, cyclopenteneoxide, etc. I

It is to be noted that the same oxyethylation agent need not be employedthroughout the'entire oxyethylation process. For instance, the secondaryamine, dioctylamine might be reacted with one mole of ethylene oxide,and two moles of propylene oxide, and such compound might then betreated with one mole of glycide and then with 2 or 4 moles of ethyleneoxide. would be equally feasible to ylene oxide and then one mole ofglycide. This same procedure could be applied just as effectively toprimary amines. Its special significance is as follows: If a secondaryamine indicated by R. is treated with 2 moles of ethylene oxide to giveN QILOCzHsOH such product could then be treated with one mole of glycideto give a diol group,'as follows:

It on Nolmooimocim R on Such product meets the requirement that, afterbeing reacted with a low molal monocarboxy acid,

there is still present an available hydroxy radical for furtherreaction, as is required in the herein described procedure.

As will be indicated hereafter, the low molal acid which reacts with analcoholic hydroxyl group, may also in turn contain areactive' hydroxylradical, as in the instance of lactic acid or hydroxyacetic acid or thelike.

For instance, reference is made to U. S. Patent No. 2,174,762, datedOctober 3, 1939, to Schuette.

et al. Said patent is concerned with oxyethylation of amines to a degreesumcient toproduce water solubility. In the present instance the numberof recurring ether linkages in any single chain is preferably limited to3 and water solu-" bility may or may not occur. In other words, anoxyethylated high molal amine whichis waterinsoluble may serve as anintermediate reactant.

See also U. S. Patent No. 2,195,194, dated March 26, 1940, to Ulrich etal. .As to methods whichcan be readily adapted for'the oxyalkyla tion ofhigh molal amines, as herein contemplated, see .U. S. Patent No.2,275,470, dated March 10, 1942, to Ruark, and U. S. Patent No.

2,337,004, dated December 14, 1943, to schwoegler. For convenience,attention is momentarily directed to the formula previously presented,to

wit:

Since available low molal hydroxy acids are comlparatively few, forinstance, lactic acid, hydroxyacetic acid, etc., and since amines arederived from hydroxystearic acid, ricinoleic acid, etc., are not asreadily available as other amines, it is ob- It use 2 moles of 'eth--Example 1 One molecular proportion of dodecylamine is caused to reactwith 2 molecular proportions of epichlorhydrin which are added to thereaction mixture in small portions, 2 molecular proportions of propyleneoxide then being brought into reaction at zero centigrade in thepresence of 0.5% of sodium ethylate. The reaction can also be conductedconveniently, if suitable caution is employed and at the sametemperature, or slightly higher temperature, by using glycide instead ofthe epichlorhydrin. This has the advantage that no hydrochloric acid isliberated to form a salt.

HIGH MOLAL AMINO-POLYGLYCOL Example 2 One molecular proportion ofcetylamine is heated in an autoclave under ressure at about 150 C. withfour molecular proportions of propylene oxide and then with twomolecular proportions of ethylene oxide. (See Examples 1 and 2 ofaforementioned U. S. Patent No. 2,174,762.)

HIGH MOLAL AMINO-POLYGLYCOL Example 3 A mixture of dicetylanddioctadecylethanolamine polyethylene glycol is obtained by the action of3 molecular proportions of ethylene oxide on about 1 molecularproportion of a technical mix ture of dicetylamine and dioctadecylamine.(See Example 1 of aforementioned U. S. Patent No. 2,195,194.) Suchproduct is then reacted further with 1 mole of glycide.

HIGH MOLAL AMINO-POLYGLYCOL Example 4 A mixture of 150 parts ofN-stearyl-B,B',B"- trihydroxy-tert-butylamine with 45 parts of ethyleneoxide (2.65 molecular equivalents) is heated in a closed vessel byraising the temperature to 120 C. uniformly during 5 hours, and thenkeeping at this temperature until the internal pressure falls to zero.(See U. S. Patent No. 2,091,105, dated August 24, 1937, to Piggott.)

HIGH MOLAL AMINO-POLYGLYCOL Example 5 One pound mole of octadecylamineis reacted with 8 moles of ethylene oxide in the manner described underExample 1 in British Patent No. 380,851 to I. G. Farbenindustrie, A.-G.,dated July 29, 1932. Attention is also directed to said patent insofarthat it enumerates other high molal basic amines suitable foroxyalkylation.

Having obtained suitable monohydroxylated, or preferably,polyhydroxylated high molal aminopolyglycols or the equivalent, of thekind previously described, such products are subjected to esteriflcationwith low molal carboxy acids having 7 carbon atoms or less, in suchpredetermined ratios thatthere is present at least one alcoholichydroxyl for subsequent esterification reactions. Monohydroxylatedcompounds require the use of a lwdroxylated low molal carboxy acid.

Some of such acids have been previously described in characterizing theacyl radical RaCO. Additional examples of the hydroxylated type havebeen mentioned. Other suitable acids include furoic and unsaturatedacids, such as acrylic, orotonic, tiglic, etc.

The esterification reactions are conducted in the usual manner. In suchinstances where there are two polyglycol radicals present, one mayintroduce a low molal acyl radical as a substituent for each terminalhydrogen atom. It is our preference to select low molal acids havingboiling points between approximately 15 and 220 C. The reaction can beconducted employing a considerable excess of such low molal acids andrefluxing at the boiling point of such acids for approximately 5 to 15hours. The reaction can also be conducted by means of an obviousequivalent such as an anhydride or other suitable derivative.

In the instance of acids having boiling points in excess of C., forinstance, normal caproic acid, it is our preference to add astoichiometric equivalent and conduct the reaction until the amount ofwater eliminated is equal to, or almost equal to, the theoretical yield.Hydroxyacetic acid may be employed in the same manner.

In the following examples, reference is made to the use of certain lowmolal acids. Actually, the esterification reaction can be accelerated bythe use of the anhydride, 1. e., ,using one mole of the anhydride toreplace 2 moles of acid, except in such instance where there is noobjection to excess acid, and where the excess acid or excess anhydrideis subsequently removed, one may replace each mole of acid by one moleof anhydride. Particular reference is con cerned with the use of aceticanhydride, propionic anhydride, n-butyric anhydride, isobutyricanhydride, n-valeric anhydride, ncaproic anhydride, and particularly thelast five, where the boiling points of the anhydrides vary from 169. Cto 242 C. When the corresponding acid is formed, such acid may serve asa reactant in the esterification reaction, or can be removed by vacuumdistillation. Reference has been made to the acids only, because theyare more generally available, but where the acyl chloride is available,the anhydride can be obtained from the acyl chlorides and the salt, orby other suitable means.

It has been pointed out that the herein contemplated amines used asreactants are basic in character. the amine and the low molal carboxyacid results in salt formation. The esterification reaction involves theelimination of water from the salt. However, the esterified amine hereincontemplated is still basic in character and combines with acids,particularly inorganic acids, to form salts. Reference to the aminesincludes the anhydro base, the hydrated base, i. e., the ammonium form,or any suitable salt, including salts of the various low molal carboxyacids'herein contemplated as reactants.

Attention is again directed to the fact that there must be a hydroxylradical left for subsequent reaction with phthalic anhydride, or itsequivalent. If all hydroxyl radicals attached to the amino compound areeliminated, then the Thus, the initial reaction between low molal acidmust contain a hydroxyl group. A mixture of low molal acids such ascaproic and hydroxyacetic may be used.

HYDROXYLATED MONOCARBOXY ESTER OF HIGH MOLAL AMINO-POLYGLYCOL 1 Example1 1 pound mole of the product described under the heading High molal'amino-nolyglycol, Example 3 is heated with 1 pound mole of isobutyricacid for approximately 8 to 18 hours at 150-154" C. The esterificationis conducted by meansof a hot condenser, that is, a condenser unreactedbutyric acid is eliminated by distillation, and if preferred, vacuumdistillation may be employed. The amount of'base required forsaponification of the ester is, of course, a means of measuring thedegree of esterification. Saponification reliberates the butyric acid,both from the salt form and the ester form. The

product shows excellentsolubility in dilute acetic acid or dilutemineral acid. The product derived from commercial raw materials is anamber-colored, viscous or sticky compound at ordinary room temperature,and if contaminated by the presence of metallic iron or the like, mayshow even a darker appearance. The inorganic salt forms are more solidin nature than the anhydro base. Such appearance is typical of theentire class of intermediate materials herein described.

HYnRoxYt/i'rEn MONOCARBOXY ESTER OF HIGH MOLAL AMmo-PoLYcLYcoL Example 2The high molal amino-polyglycol described under the heading of Example 1is substituted for the high molal amino-polyglycol used in the precedingexample.

HYDROXYLATED MONOCARBOXY ESTER or HIGH MOLAL AMINO-POLYGLYCOL Example 3The same procedure is followed as in the preceding example, except thata product of the kind described under the heading High molalamino-polyglycol. Example 2" is substituted for the amino-polyglycolemployed in the previous example.

HYDROXYLATED MONOCARBOXY ESTER or HIGH,

MOLAL AMINO-POLYGLYCOL Example 4 Esterification is conducted by means ofan acid havinga substantially higher boiling point, such as normalcaproic acid. One may use more than 1 mole of acid, provided there arepresent at least 3 hydroxyl radicals per mole of aminopolyglycol. Thetemperature of esterification is approximately 175-l95 C., and thecondenser employed is a cold condenser with suitable arrangement to trapthe water of esterification as formed, and also return any unreactedacid for further reaction. (Such arrangement is suitable where the acidis volatile and water-insoluble.)

There is no difliculty in regard to the loss of the low molal acid,because, although it is volatile at the indicated temperature, yet it isreadily condensable. Thus, as specific procedure illustrating thepresent example, one may use 1 mole of amino-polyglycol, Example 3, 1mole of caproic acid.

HYDROXYLATED MoNocARBoxY ESTER or Hion MOLAL AMINO-POLYGLYCOL Example 5The same procedure is employed as in the previous example, except thatanhydrous hydroxy-- acetic acid is employed instead of caporic acid.

Previous reference has been made to high molal amino-polyglycols asreactants, for the reason that it is our preference to employ productsin which there is at least one ether linkage obtained by the use of 2 ormore moles of ethylene oxide per aminohydroxy atom. If desired, however,one may employ a single mole of the oxyethylating agent, such asethylene oxide, for each available aminohydrogen atom. In such event,the

product obtained is not a Polyglycol, but an aminoalcohol, insofar thatthere is a single alkylene radical present and no ether linkage. Suchtype of reactant may be employed in the present instance, if desired.Regardless of what type of reactant is emplo'yed, the final product isinvariably soluble in or produces a colloidal sol in dilute acetic acidor dilute mineral acid. Completeness of reaction can be checked in eachinstance in the manner previously indicated.

In the case of hydroxyacetic acid, one may-use a distinctly highertemperature without volatilization of the acid than in theinstanceslwhere caproic acid is employed. For instance, theesterification involving hydroxyacetic acid may employ a temperature ashigh as 215" C.

Manyof the preceding examples will be found to be soluble in water, evenin the absence of acid. Some of the products are soluble in or produce aturbid sol or suspension in gasoline or benzene.

Previous reference has been made to the use or the anhydride as anacylating agent instead of the free acid. Probably salt formation iseliminated until esterification begins with liberation of a molecule ofacid for each molecule of anhydride added. The liberated acid acts, oicourse,

as if it had been added at thebeginning of the reaction, andadditionally, presents a modification, in that water is not eliminated,unless esterification takes place by virtue of the free acid.,

If, however, the esterification reaction involves only the anhydride andno acid, waterwould not be liberated. Thus, the measurement of thecondensed water, if any, under such circumstances,

is not necessarily an index of esterification. Other procedure must beused, although unforturnately, no method of measurement is availablewhich is relatively quick and absolutely sat-Y isfactory to a preciseand quantitative degree;

If a salt is formed, titration with caustic sodav or potash converts thesalt intothe free base. The particular end point using the usualindicators is rather indefinite, and thus, the use of additional alkalito determine the saponification value results in a determination ofsomewhat approximate value, due to such diificulties of manipulation.The values obtained, however, even though only approximate, areperfectly satpreceding, and

analytical isi'actory for the present purposes. Other suitable procedurebut more laborious, involves the saponiilcation oi the product, followedby acidiflcation with a non-volatile mineral acid, e. g., sulfuric acid,and distillation of the low molal carboxy acids which were originallycombined in ester form, followed by the usual volumetric procedure incorrelation to the original sample.

The following reactions illustrate the formula of the high molalaminoalcohols and aminopolyglycols, and also their esterificationproducts, without reference to. the formation of the hydrated base or ofa salt from the anhydro base. In the subsequent structural illustrationswhere R1 appears, it is assumed, for convenience,-that R1, in suchinstance as illustrated, does not include a hydroxyl radical.Oxyalkylation, under such circumstances, must, of necessity, involve theamino hydrogen atom. Actually, it would not matter it the radicalindicated by R1 does contain a hydroxyl radical, tor the reason that thelinkage involving a hydrogen atom and an amino nitrogen atom, ascontemplated in the herein described reactants, appears to be moresusceptible to oxyalkylation than the hydrogen-oxygen linkage of thehydroxyl group. After the first mole of oxyalkylating agent isintroduced into the amino hydrogen position, whether it be ethyleneoxide or glycide, the resulting radical is the equivalent of R1 in suchinstances where R1 does contain an alcoholic hydroxyl group. It wouldnot matter if the next mole of oxyalkylating agent attacked the hydroxylof R1 or the hydroxyl oi the alcoholic group which replaced the aminohydrogen atom. Stated in another way, if R1 is a hydroxylated radical,then RzOI-I and R1 would be the equivalent of each other, and RaCOOH inthe resulting esteriflcation reaction would combine as readily, in mostinstances, with the R1 radical as with the RzOH radical. One must notlose sight of the fact that esterification must involve a tertiaryamine, and thus eliminate amidification as a possible reaction. If R1does contain an alcoholic hydroxyl and is reactive, and if the amine isthe secondary amine, then in each instance the reaction must beconducted by the use of suitable quantities of an alkylating agent so asto eliminate the amino hydrogen atom.

1 a I R \NH 0,1140 nomion R1 R;

rclmotfa H 00.11.

NCxHs n RI 0(CH|O)1H n o o,Hlo)2oc.R='

NCaH

R1 winio'hn 2n 0 H noioc R.

ocln a 011 NCaHs I /O:H 110100.11: R

l OClHI I OCaHa OH NCaHs 000.11.; R. 1

OCaHa "1 21 o,Hl0).;'H 110500.11, (CIHAO)JOC-RS I l I RN RN (C:H40)$H 2|Qh 22- /O!'H 110E003, 000.11,

C3H5\\ I "E CJHB OH on RN RN or HOEOCLR; 000.12,

cin can on OH As will be noted, in such instances where butylene oxidereplaces ethylene oxide, the number of carbon atoms in the polyglycolradical attached to the amino nitrogen N may be as high as 15.

In certain of the above formulae at first examination there does notappear to be available hydroxyl to act as an alcoholic compound insubsequent esterification reactions. However, it has been pointed outthat the radical R3 may contain an alcoholic hydroxyl radical, as in thecase of lactic acid or hydroxyacetic acid, and similarly, one occurrenceof R in such instances where there are two occurrences of R joined to anaminonis trogen atom may represent a hydroxyalkyl or .polyhydroxyalkylradical, including the type in which the carbon atom chain isinterrupted by oxygen. This is illustrated by reference to the firstfour reactions by merely replacing the secondary amine (R)'2NH by theprimary amine RN (H): by using an appropriate amount of oxy-.

ethylating agent to convert such primary amine into a secondary amine.

Summarizing what has been said thus far, it

is to be noted that in essence it represents nothing more nor less thana description of a basic amino-alcohol of the formula:

ether linkages and having at least 8 carbon atoms and not more than 32carbon atoms, and

- carbon radicals having atoms, and the monovalent radical HORa, whereone ethylene linkage is present. is obtained at a distinctly highertemperature being a member of the class consisting of all-- phatichydrocarbon radicals, alicyclic hydrocarbon radicals, and aralkylhydrocarbonradicals; R2 is a divalentradical having less than 16 carbonatoms and not more than 3 ether linkages and being a member of the classconsisting of alkylene radicals, hydroxyalkylene radicals, a rlkyleneoxyradicals, hydroxyalkyleneoxy radicals, polyglycol and hydroxy polyglycolradicals, in which any alkylene radicals present are selected from thegroup consisting of ethylene, .propylene, butylene, and methylbutylene;and R1 is, a monovalent radical and a member of the class consisting ofaliphatic hydrocarbon radicals, alicyclic hydrocarbon radicals andaralkyl hydronot more than 32 carbon in R2 has its prior significance;RaCO is radical of a low molal monocarboxy acid less than 8 carbon atomswith the added that at least'one of the 3 radicals, R1, R2 and R3 shallhave present an alcoholic hydroxyl radical.

Previous reference has been made to the use of a polycarboxy reactant.Such intermediate reactants are readily available and are produced byreactions involving suitably selected fatty compounds or theirequivalent with typical polybasic carboxy acids, such as phthalic acid,succinic acid, malic acid, fumaric acid, citric acid, maleic acid,adipic acid, tartaric acid, glutaric acid, diphenic acid, naphthalicacid, tricarballylic acid, etc. Instead of acids one may, of course, useany an acyl having proviso functional equivalent, particularly the anhydride. The anhydride, as a primary reactant, when available, is aparticularly suitable reactant when two carboxylreactants are attachedto adjacent carbon atoms. The most suitable acids are maleic, citraconicand phthalic. 'They are conveniently used in the form of the anhydride.Acids having three or more carboxyl radicals may be used, but we preferto use the dibasic carboxy acids. Hydroxylated polycarboxy acids may beemployed, but we prefer to use the nonhydroxylated type, insofar thatthey are, generally speaking, more resistant to pyrolysis.

Another type of polybasic carboxy acid which may be employed, isthe-so-called adduct type. For instance, maleic anhydride or itsequivalent is reacted with a number of well known types of reactantswhich contain conjugated double bonds and enter into the dienesynthesis. The Diels- Alder adducts thus obtained representfsuitablepolybasic carboxy acids.

The somewhat similar adduct, in the sense that it involves the use ofmaleic anhydride or its equivalent, is the Clocker adduct. This isobtained from unsaturated acids, alcohols, or the like, which may haveonly one ethylene linkage, or is not conjugated in the event that morethan The adduct than the Diels-Alder adduct and appears to be acyclic.Cyclobutane structures may also be involved. In the event that eithertype of adduct is obtained from a detergent-forming monocar boxy acid,particularly a higher fatty acid such as the fatty acids derived fromChina-wood oil or linseed oil, the product so obtained is not consideredas a detergent-forming acid derivative,

orv a higher fatty acid derivative in the present instance. I

It has been previously pointed out that the acylated amino-alcoholsemployed as reactants must have present a reactive alcoholic hydroxylradical, and may have present more than one such hydroxyl radical, andtwo, three, or even more. In light of this fact, it is obvious that onemay produce monomeric compounds comparable to dibutyl phthalate orlinear polymers free from cross-linking as obtainable from ethyleneglycol and phthalic anhydride, or else compounds in which cross-linkingcan take place to a greater or lesser degree, comparable to thoseobtainable from glycerol and phthalic anhydride. In any event, the finalproducts obtained by esterification, must represent monomeric compounds,or else, polymeric compounds comparable to an A stage, or "3 stageresin, i. e., either they must be still fusible or soluble in selectedsolvents, or both. They must not represent the insoluble, infusible Cstage resin.

Esterifications of this type are used so generally that furtherdescription appears unnecessary. The alcoholic reactant, i. e., theaminoglycol, is usually a fairly viscous or semi-solid material per se.Reaction with polybasic carboxy acid derivatives, as described, producessubstances which may be viscous liquids, balsams, or hard solids, but inany event, they are sub-resinous in the sense that they have not reachedwhat is commonly termed the stage.

Esterification reactions, of course, are cone ducted in such a mannerthat an active carboxyl group, or its equivalent, is present as anavailable active hydroxyl group. The reactions may be, and frequentlyare, catalyzed by the addition of a small amount of free acid, such asdry hydrochloric acid, a few percent or less of an aromatic sulfonicacid such as paratoluene sulfonic acid. The temperature employed isabove the boiling point of water, for instance, 160 to 180 C., or evenhigher, provided there is no pyrolysis. The reaction goes to completionby virtue of the fact that water of esterification, or its equivalent,is removed. Such water may be removed in any suitable manner, such asthe passage of dry nitrogen gas, or by the use of an inert solvent suchas xylene or decalin. The progress of the reaction can be checked bydetermination of the amount of free acid present.

Since the herein described compositions of matter and particularly thoseemployed as a demulsifying agent, are obtained by esterificationreactions involving an acidic fractional ester, as previously described,and since such fractional ester in turn is derived by esterificationreactions between (l) compounds containing a detergentformingmonocarboxy acid and (II) a polybasic carboxy acid, it is necessary thateither (I) or (II) contain an alcoholic hydroxyl group. Such alcoholichydroxyls are present in some detergent-forming acid molecules, and whensuch acids are employed, they may be esterified directly by thepolybasic acid. Obviously, the esters, salts, and other derivatives ofsuch acids which leave the hydroxyl part of the acyl group intact, mayalso be employed. Examples of suitable hydroxy detergent-forming acidsor their functional equivalents are: Hydroxystearic acid, ricinoleicacid, trihydroxypalmitic acid, hydroxynaphthenic acid,tridihydroiwstearin, triricinolein, butyl ricinoleate, ethyldihydroxystearate, ethylene glycol diri'cinoleate, etc. Hydroxylatedpolybasic carboxy acids may react with any high molal acids.

In some cases it is desirable to form a partial ester of these hydroxydetergent-forming acids with a polyhydric alcohol to yield a compoundhaving more than one hydroxyl group available for reaction with thepolybasic acid. Examples of such esters are: Glyceryl monoricinoleate,glyceryl diricinoleate, ethylene glycol monodihydroxystearate,diethylene glycol monohydroxystearate, sorbitol di-dihydroxystearate,etc.

In addition to the common higher fatty acids and other detergent-formingacids described above, thepresent invention is intended to include, forthe manufacture of the intermediates, the use of fatty acids and partialesters of fatty acids obtained by the drastic oxidation of non-dryingand semi-drying oils, such as castor oil, sunflowerseed oil, cottonseedoil, rapeseed oil, soyabean oil, etc. Acids and esters prepared fromsuch blown or drastically-oxidized oils are regular articles of commerceobtainable on the market. Other detergent-forming acids suitable forpreparing the resent demulsifying agents may be prepared by blowing oroxidizing unsaturated fatty acids, such as castor oil fatty acids, soya-'bean fatty acids, oleic acid and the like.

When the detergent-forming acid itself does not contain an alcoholicgroup, it may be reacted with a polyhydric alcohol to yield a partialester having one or more residual hydroxyls available for esterificationwith a polybasic acid. Note what has been said in regard to reactionwith hydroxylated polycarboxy acids.

Conversely, the polybasic acid used may first be esterified with thepolyhydric alcohol to yield esters having unreacted hydroxy groupsavailable for esterification of the detergent-forming acid. If thedetergent-forming material does not contain an alcoholic hydroxylradical, we have found that the reaction is usually easier to control,in order to obtain the desired final products,

if the polyhydric alcohol intended to be used is first reacted with thedetergent-forming acid and the fractional ester so obtained subsequentlyreacted with the polybasic acid.

Examples of polyhydric alcohols which may be employed to bring aboutester formation between detergent-forming acids and polybasic acids are:Glycerol, diglycerol, alpha-beta, gamma butanetriol, beta methylglycerol, ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propene diol, isobutylene glycol, ethylene glycol gycerol ether,diglycerol monoethylene glycol ether, mannitol, sorbitol, sorbitan,mannitan, sorbitol monobutyl ether, erythritol, adonitol, dihydroxythiophene, etc.

For the purpose of this invention, polyhydroxy amines are considered thefunctional equivalents of polyhydroxy alcohols. Examples of suchcompounds are: Monoglycerylamine, triethanolamine, diethanolamine,phenyldiethanolamine, dicyclohexanolamine, cyclohexylpropanola'mine,benzyldiethanolamine, pentanolamine, diethanolmethylamine,tripropanolamine, etc. Ethers derived from this class of compounds or incombination with the previously mentioned diols, triols, etc., areincluded.

It should be pointed out that the hydroxy esters conveniently employedfor reaction with polybasic acids to form the intermediates of thepresent invention, need not necessarily be prepared by reacting thedetergent-forming acid with the polyhydric alcohol directly. In manyinstances, it is more convenient to prepare these 'hydroxy esters byre-esterification of fats, oils, drastically-oxidized oils, ordetergent-forming acid esters with polyhydric alcohols. For example, afat such as stearin may be re-esteriiled with 7 slycerine to formglycerol monostearate, which and such products may f page '7, headingpie 1.

maybe subsequently reacted with a polybasic acid. The preparation ofsuch fractional esters derived from fats, oils, and drastically-oxidizedoils, is well known, and the products are sold commercially undervarious names. Similar products may be obtained by re esteri fication ofthe oils, fats, drastically-oxidized oils, and detergent-forming acidesters with other polyhydric alcohols, such as glycols, sorbitol,mannitol, polyhydroxyamines, or other polyhydric alcohols; beconveniently employed for the manufacture of the demulsifying agents ofthe present process. Analogous partial esters are obtained from rosinacid, naphthenic acid, and the like.

Often it is convenient to perform the re-esterification simultaneouslywith the esterification of the polybasicacid. For example, a mixture ofa fatty oil, a polyhydric alcohol, and a polybasic acid may be mixed andheated together to yield an intermediate. If a hydroxylated oil, suchas, for example, triricinolein, is employed, then one need not add apolyhydric alcohol unless desired.

The formation of one kind of intermediate contemplated for use accordingto our invention, may be exemplified by the esterification reactionbetween a polybasic acid and ricinoleic acid.

'In this case the detergent-forming acid com- 7 pound contains a singlehydroxyl group, and the reaction obviously will yield a simple estercontaining a residual carboxylic acid group, but no v residual hydroxylgroups. v

The formation of a second type of product may be exemplified by thereaction between ethylene glycol monostearate and a polybasic acid. Inthis case, as well, the result of reaction is a simple ester containingone or more residual carboxyl roups.

Our preferred reactants of the acidic fractional ester type are derivedfrom castor oil and phthalic anhydride. Such compositions per se areold.

For instance, see 'U. s. Patent No. 2,166,432,

dated July 18, 1939, to De Groote, page 4, from the heading to page 5,heading ample 1. July 18, 1939, to De Groote, page 4, from the headingIntermediate amine, Example 8, to

Composition of matter, Exam- Composition of matter, Ex-

' onnoooonz then reaction products of phthalic anhydrideor phthalic acidmay be indicated in the following manner, although, for purposes ofconventhe usual isomer, where, of course, the two carboxyl radicals areattached to adjacent carbon atoms:-

coon' C00.R.COO.CH2

H.R.COO. H,

Intermediate amine, Example 9,

See U, S. Patent No. 2,166,433, dated indicated by the followingSimilarly, one

monohydric alcohols, for instance, ethyl ricin-, oleate, 'propylricinoleate, sodium ricinoleate, amylamine hydroxystearate, etc. It isintended ience, phthalicacid is not shown in the form of COOH CQOH.

ooon COOH 0oo.R.000.cH, I

A large number diately present themselves, for instance, esters derivedby reaction with ricinoleic acid, hydroxy stearic acid, dihydroxystearicacid, and the like; or the corresponding esters derivedfrom glycols orglycol ethers, such as ethylene glycol or diethylene glycol, whichcontain no free hydroxyl radicals attached to the glycol radical orresidue. might have products derived from to include blown oils.

In the examples shown above, where the ester is polybasic, for instance,compounds of the type exemplified by C and D, above, one might removethe acidity of one of the carboxylic hydrogen atoms, or two of thecarboxylic hydrogen atoms, in any feasible manner, i, e., byneutralization with an alkali, or by conversion into an ester involvingreaction with anew kind of an alcohol, 1. e., a monohydric, dihydric,trihydric, etc.

, t In the case of D, above, two carboxylic hydrogens may beneutralized.- In any event, however,

the material derived by reaction between a polybasic acidand itsfunctional equivalent and a hydroxylated fatty material of the kinddescribed, is characterized by the presenceof at least one free carboxylradical. j

Where reference is made to ricinoleic acid,

hydroxystearic acid, dihydroxystearic acid, a-

hydroxy fatty acid, and the like, it is evident that certain simplederivatives, such as the halogenated compounds, etc. are the obviousfunctional equivalents; for instance, chlorinated triricinolein, may

Brominated tions of the kind indicated, still has the same of related Yproducts be employed instead of triricinolein. Brominated ricinoleinacid might be eminstead of functional properties as the unmodifiedhydroxyh ated fatty material, and thus acts in the same manner, as faras roducing an effective demulsifying agent is concerned. In the heretoappended claims reference to a hydroxylated fatty material includes suchobvious functional equivalents.

The second of the aforementioned De Groote patents describes suchmaterials as diphthalated diricinolein, dimaleated monostearin,dioxalated monoabietin, dicitrated mononaphthenin, etc.

In such instances where phthalic anhydride or the like is reacted withricinoleic acid, hydroxystearic acid, etc., to form a fractionalester,such fractional ester is reacted further with the hydroxylatedamino-alcohol without limitation as to whether the carboxyl group of thephthalic acid radical or the carboxyl group of the higher fatty acidradical is involved.

Although the compounds or compositions of matter herein described may beobtained in any suitable manner, it is obvious that having obtained ahydroxylated amino-alcohol of the kind described, all that one need todo is to react such compound with the acidic fractional ester of thekind previously described, in order to produce compositions of the kindherein contemplated. Such reactions are illustrated by the followingexamples:

Comosrrron or m'r'ran Example 1 1 pound mole of a material of the kindexemplified by Hydroxylated monocarboxy ester of high molalamino-polyglycol, Example 1, is esterifled with 1 pound mole of thedibasic ester obtained by reacting 1 mole of castor oil with 2 moles ofphthalic anhydride. Such product is essentially triricinolein di-acidphthalate. The reaction is conducted at 165 to 195 C. for 2 to 6 hours,until analysis shows that one carboxyl has been eliminated byesterification. The reaction is a conventional esterification reactionand can be conducted in the presence of an inert solvent, such as xyleneor decalin, which removes the water in a slow manner. The method ofconducting such esterification reactions is the same as has beenpreviously described in detail. The product obtained is a thick,viscous, subresinous, deep amber-colored mass.

Comosrrrou or Mlrr'rm'i Example 2 The same procedure is followed as inExample 1, immediately preceding, except that triricinoleintri-acid-phthalate obtained by reacting 1 mole of castor oil with 3moles of phthalic anhydride, is employed instead of triricinoleindi-acid phthalate.

Coueosmox or Mar-rm Example 3 The same procedure is employed as in thepreceding example, except that the time of reaction is increasedsomewhat and temperature of reaction increased somewhat, for example, upto 200 C., and as long as 6 to 8 hours, to insure elimination ofone-half to two-thirds of the acid value, due to the phthalic anhydridecarboxyls.

COMPOSITION or MATTER Example 4 The same procedure is employed as inpreceding Examples 1 to 3, inclusive, except that materials of the kindexemplified by "Hydroxylated monocarboxy ester of high molalamino-polyglycol, Examples 2 to 5, inclusive," are substituted in placeof the material described under the heading Hydroxylated monocarboxyester of high molal amino-polyglycol, Example 1.

Comosrrron or Manna Example 5 Comrosrrrox or Mama Example 6 The sameprocedure is followed as in Examples 1 to 5, immediately preceding,except that an analogous maleic anhydride, adipic acid, citraconicanhydride,- succinic acid, or some other polybasic acid, particularly adibasic acid, is substituted for phthalic anhydride derivatives in thepreceding examples.

In order to illustrate derivatives obtained by reaction between apolybasic carboxy acid fractional ester, and more especially, a dibasiccarboxy acid fractional ester and an esterified amino-alcohol of thekind described, the following formulae, along with indicated reactions,are included. Previous reference has been made to Ra.COOH, being a lowmolal monocarboxy acid. In some instances, such acid might contain analcoholic hydroxyl group, as in the case of lactic acid, hydroxyaceticacid, etc. For convenience in the formulae appearing immediatelyhereafter OHR'3.COOH is intended to refer specifically to the low molalmonocarboxy acid having an alcoholic hydroxyl radical. Previousreference has been made to various types of fractional esters containinggroups derived from polybasic carboxy acids, and particularly, dicarboxyacids. If a compound such as monostearin is reacted with two moles ofphthalic anhydride, the resultant fractional ester is, in reality; theequivalent of the dibasic acid. The same applies to the dibasic reactionproduct obtained from 1 mole' of triricinolein and 2 moles of phthalicanhydride. A similarv reaction product derived from 3 moles of phthalicanhydride, would represent a tribasic acid. The same is true of 'aproduct derived from 3 moles of phthalic anhydride and 1 mole ofmonoricinolein.

For convenience, the formulae are limited to the dicarboxy typeHOOC.R4.COOH, in which R; may be considered the nucleus or radicalderived from triricinolein diphthalate or monostearin diphthalate. Theformulae are based on reactions involving equimolar quantities, exceptin the last two instances, where 2 moles of the dicarboxy isomers ormore complex structures may be involved when R; contains one or morealcoholic ovelie t what has been said, except to point out m RN(C,H);OO.B';0H 0

l tw ak- Y l o n 1 R B a \(mmonoccaooc'lacoon 3, 1;, oocnlcoon u 3 65 2a 000.12. mcmloncm 7 m on Bl B v a ooc.n'.oocn lcoon \(cnnonc l oocmcoona common a n 0003.. lc-momm v N mnmfl m n on oocmaoocmdoon v onulcimohclm 1: 000.12. 12/ I on )mcmohc 1a a O'm/OOC-R'IOH V 1:,0002.000: R/ on I 4 n owmmnomm n oocal'loocnlcoon' c e mcim I v11.olclmonn' I m oocnlcoon n olcmlonoanl so u n 'oocnaon NC|B (call0).c-mn. ommo ocnlcoon n. on 5 00-03 e v n oocnz'loocnlcoon oc v lclnlolaclm.on l a oocnlcoon B/ 000.2. Previous reference has been made to the {or-R 0c 1 4o mula:

on o 1 n\' oo0.nioocn.coon

0C 3: OH

uclm Examination reveals that reaction may have involved the otheravailable hydroxyl radical, thus ocm resulting in a. compound of thefollowing for- I V oocmcoon mm: r 0 3 000415011 0 (women. (61340}!0CB8 cK F a, oocnvcoon 7 (mom! (cmonocmcoon mamolnruelnregardwmemuowln mm cos7 c 7 0003' pound previously depicted and its isomer.

1? on I oocmcoon n oocazaoocmooon 000.12. 000 in \N(O:H4O)IH Y c c m 01!onoocmcooav a common I s n n Nwfliloicam V lwlmooom'lon Gmooom0ocmc0onas 0 40 0 V I Any of the previous compounds illustrate hyo n droxy'acids which may undergo-condensation lclmmloc n'lon polymerization, andthus form compounds or inw 10 creased molecular weight, Compare with theRI v r 1 tormatlon of linear polymers, 101- example, from nethyienezlycol mono-acid phthalate. 'i'rlhydric l alcoholicstructureoithe useoiatribasic acid :BOhQC.RsOOCR CO'OH would em to cm II v In any evcnt,'thc formation of the polymers may be indicated as aderivative of the prior com- P und of the formula:

a oocnaoocalcoon .Cs n

R1 OH in the following manner:

a oocnaooomcoon .Cr I\ R: 11]

noocmcoo.a';.coo n ""i I oinm 'i H:O Bi i a oocnuoocmooion; .Cfl; l.

inoiommcoomooo R i.----! /CaHs no R;

In the above presentation re-esterification has been ignored.

The esterified hydroxylated amino -glycol of the kind previouslydescribed, must contain at least one, and preferably more than one,alcoholic hydroxyl radical, Such reactant may be considered for the sakeof simplicity as being in the class of an alcohol, 1. e., a monohydricor polyhydric alcohol. If an alcohol is indicated by the formula Y'(OH)n, where 1: indicates the number 1 or more, and if a polybasic acid bodybe indicated by the formula xwcoonm where n indicates the number 2 ormore, then the reaction between a monohydric alcohol and a polybasicacid will result in a compound which may be indicated by the followingformula: YX(COOH) 1# where n indicates the number 1 or more, and whichis, in reality, a contraction of a more elaborate structural formula, inwhich X and Y are joined by a carboxyl radical or residue. Assuming,however, as would be true in the majority of cases, that the alcoholactually would be a polyhydric alcohol, and that the acid body would bepolybasic in nature, for instance, if one employed a diphthalate ortriphthalate, then examination reveals that the formulae might result ina combination, in which there were neither residual carboxyl radicals,nor residual hydroxyl radicals, or might result in compounds in whichthere were residual bydroxyl radicals, and no residual carboxylradicals, or compounds where there might be residual carboxyl radicalsand no residual hydroxyl radicals, or there might be both. This isindicated by the following:

in which q indicates a small whole number (one in the case of a monomer,and probably not over 20, and usually less than and m and n indicate thenumber 1 or more, and m" and n" indicate zero or a small ormoderately-sized whole number, such as zero, 1 or more, but in anyevent, probably a number not in excess of 40. Naturally, each residualhydroxyl could combine with a phthalic acid radical or its equivalent,or with a tribasic acid radical, such as one derived from citric acid;and in such event, there would be a large number of free or uncombinedcarboxyl radicals present, possibly 1 to 20, or more. Actually. thepreferable type of reagent would be more apt to include less than 10,and in fact. less than 5 free hydroxyl radicals. It is not necessary toremark that the residual carboxyl radicals can be neutralized in anysuitable manner, such as conversion into salts. esters, amides, aminoesters, or any other suitable form. Usually, such conversion into saltform would be by means of sodium hydroxide, potassium hydroxide, calciumhydroxide, magnesium hydroxide. ammonium hydroxide, amylamine,butanolamine, ethanolamine, diethanolamine, triethanolamine, cyclo-'citric acid compound. Similarly, as has already been pointed out, alarge number of molecules of a polybasic'acid compound might combinewith a single molecule of a highly hydroxylated aminoalcohol derivative.For practical purposes, however, we have found that the most desirableproducts are obtained by combinations, in which the ratio ofaminoalcohol derivative to the polybasic acid is within the ratio of 3to 1 and 1 to 5, and in which the molecular weight of the resultantprod- 85' net does not exceed 10,000, and is usually less than 5,000, orpreferably, less than 3,000. This is particularly true, if the resultantproduct is soluble to a fairly definite extent, for instance, at least5%, in some solvent, such as water, alcohol, benzene, dichlorethylether, acetone, cresylic acid,'or the like. This is simply another wayof stating that it is preferable, if the product be one of thesub-resins, which are commonly referred to as an A resin, or a B resin,as distinguished from a C resin, which is a highly infusible, insolubleresin (see Ellis Chemistry of Synthetic Resins, 1935. page 862 et seq).

In recapitulating what has been said previously, the sub-resinous,semi-resinous, or resinous product herein contemplated may be indicatedby the following formula:

in which the characters have their previous significance, and yrepresents a small whole number not greater than 3, and :it' representsa small whole number not greater than 5; Z represents a hydrogen ionequivalent, such as a metallic atom. organic radical, etc.

Reference to an amine and amino compound is intended to include thesalts and the anhydro base, as well as the hydrated base, since bothobviously are present when a water-containing emulsion is treated withan amine or amino compound.

In an aqueous solution of the amine the anhydro base, R-NH2, thehydrated base. RNH3OH, and the two ions are all present. (Richter, v. s.page252.)

In the hereto appended claims reference to radicals derived from olefineoxides, is intended to include glycide. In other words, in the case theapplication of asphalt in road building and the like; as a constituentof soldering flux preparations; as a flotation reagent in the flotationseparation of various minerals; for flocculation and coagulation ofvarious aqueous suspensions containing negatively charged particles,such as sewage, coal washing waste water, and various trade wastes, andthe like; as germicides, insecticides, emulsifiers for cosmetics, sprayoils, waterrepellent textile finish, etc; These uses are by no meansexhaustive. The most important phase of the present invention, as far asindustrial application goes, is concerned with the use of the materialspreviously described as demulsifiers for water-in-oil emulsions, and'more specifically, emulsions of water or brine in crude petroleum.

We have found that the chemical compounds herein described, which areparticularly desirable for use as demulsifiers, may also be used as abreak inducer in doctor treatment of the kind intended to sweetengasoline. (See U. 8. Patent No. 2 ,l57,223, dated May 9, 1989, toSutton.)

Chemical compounds of the kind herein described are also of value assurface tension de-i pressants in the acidization of calcareousoilbearing strata by means of strong mineral acid, such as hydrochloricacid. Similarly, some members are effective as surface tensiondepressants or wetting agents in the flooding of exhausted oil-bearingstrata.

As to using compounds of the kind herein described as flooding agentsfor recovering oil from subterranean strata, reference is made to theprocedure described in detail in U. S. Patent No. 2,226,119, datedDecember 24, 1940, to De Groote and Keiser. As to using compounds of thekind herein described as demulsifiers, or in particular as surfacetension depressants, in combination with mineral acid or acidization ofoil-bearing strata, reference is made to U. S. Patent No.

2,233,383, dated February 25,1941, to De Groote and Keiser.

The newcompounds herein described are of utility, not only for thepurposes specifically enumerated in detail, but also find application invarious other industries, processes, and for various uses where wettingagents of the conventional type are used. As to some of such additionaluses which are well known, see The Expanding Application of WettingAgents, Chemical Industries, volume 48, page 324 (1941).

Since the herein contemplated products are esters, it is hardlynecessaryto point out that saponificatlon decomposes the product intoits original components, to wit, an amine and an Actually, the acids areobtained acid or acids. in the form of salts, usually the sodium orpotassium salts. Such conversion into the original components or simplemodifications thereof results in products which can be examined in thecustomary manner, and thus serve to identify the esterified aminoradical.

Having thus described our invention, what we 1 claim as new and desireto secure by Letters 1 Patent is:

, 32 carbon atoms; said detergent-forming acid 1. A sub-resinousesterification product of the formula:

radical having (a) an unreacted carboxyl radical; and (b) adetergent-forming monocarboxy: acid radical having at least 8 and notmore than radical being an integral part of a detergentformi'ngacidcompound of the class consisting of acids, monohydric alcohol estersand polyhydric alcohol esters, and 1/ represents a whole number from 1to 3, and 3: represents a whole number from 1 to 5, and n, m and mrepresent whole numbers from 0 to 40; q represents a whole-number from 1to 20; z is a hydrogen ion equivalent; Y is the radical of a basicesterified amino-alcohol of the formula:

R mmoocm .r in which R is a monovalent radical free from either linkageand having at least 8 carbon atoms and not more than 32 carbon atoms andbeing a member of the class consisting of ali-' cals, polyglycol andhydroxypolyglycol radicals in which any alkylene radicals present areselected from the group consisting of ethylene, propylene, butylene, andmethylbutylene; and R1 is a monovalent radical and a member of the classconsisting of aliphatic hydrocarbon radicals,

alicyclic hydrocarbon radicals, and aralkyl hydrocarbon radicals havingnot more than 32 car bon atoms and the radical HORz, wherein R2 has itsprior significance; RaCO is an acyl radical of a low molal monocarboxyacid having less than 8 carbon atoms; with the added proviso that atleast, one of the 3 radicals, R1, R2 and R: shall have present analcoholic hydroxyl radical.

2. The product of claim 1, wherein the polybasic acid radicalsarelimited to they dicarboxy species.

3. The product of claim 1, wherein the polybasic acid radicals arelimited to the dicarboxy species, and in' which there is at least onealcoholic hydroxyl radical present as part of the radical R1.

4; The product of claim 1, wherein the polybaslc carboxy acid isphthallc acid and in-which there is at least one alcoholic hydroxylradical present as part of the radical R1.

5. The product of claim 1, wherein the polybasic carboxy acid is maleicacid and in which there is at least one alcoholic hydroxyl radicalpresent as part of the radical R1.

